Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups

Definitions

• the invention relates to a process for the preparation of storage-stable, crosslinkable high molecular weight silicone resins by the reaction of at least two different silicone resin oligomers containing alkoxy groups and optionally also hydroxyl groups, by copolymerization with a polyhydric low molecular weight alcohol, and their application to
• No. 4,899,772 A teaches condensation-curing compositions for abhesive coatings which consist of a reactive crosslinked and a reactive linear polyorganosiloxane.
• the reactive crosslinked polyorganosiloxane is obtained by reacting an alkoxy-functional, silanol-free crosslinked polyorganosiloxane with a polyhydric alcohol in the presence of a transesterification catalyst at a temperature of 100 to 160 ° C such that the molar ratio of Si-bonded alkoxy groups to carbinol groups of the polyhydric alcohol selected from 0.8: 1 to 1.2: 1, the reaction driven to a degree of conversion of 25% to 90% and then
• the polyhydric alcohols are polyester polyols, i. Ester group-containing polyols, which by
• EP 0017958 A1 teaches condensation-curing compositions for abhesive coatings consisting of a reactive cross-linked and a reactive linear polyorganosiloxane, the relative amounts of linear to cross-linked polyorganosiloxane differing from those of US 4,899,772 A.
• condensable preparations according to EP 0017958 A1 consist predominantly of the thermosetting silicone resin in addition to 0.05 to 4% of the linear polyorganosiloxane.
• Siloxane components namely a linear and a
• Chlorosilane precursors by hydrolysis and condensation
• crosslinkable polyorganosiloxanes according to US Pat. No. 4,749,764 A form tack-free films, there is a difference between the pure in
• the object of the present invention is to overcome the disadvantages of the prior art and to provide crosslinkable Polyorgano siloxanes, which have a good shelf life with a high reactivity and with which hard, anti-corrosive coatings, which at temperatures between 10 ° C and 25 ° C to cure quickly and lead to tack-free, smooth coatings are obtained.
• the object is achieved by the invention.
• the invention relates to a process for the preparation of crosslinkable silicone resins in that, in a first step, a mixture of at least two different silicone resin intermediates (A), the Si-bonded alkoxy groups and optionally
• R is the same or different and denotes a monovalent, SiC-bonded, optionally substituted C 1 -C 20 -hydrocarbon radical,
• R 1 is the same or different and is a hydrogen atom or
• R 2 is the same or different and is a monovalent C 1 -C 6 -alkyl radical
• a and b are each a number in the value of 0, 1, 2 or 3 each
• silicone resin intermediates (A) contain at most 10 wt .-% Si-bonded hydroxyl groups
• silicone resin intermediates have a molecular weight M w of 600 to 2,500 g / mol
• Reaction mixture is preferably distilled off, wherein
• R and R 1 have the meaning given above and
• c and d are each a number in the value of 0, 1, 2 or 3 each
• c has the value 1 in at least 30% of all repeat units of the formula (1) and c has, over all repeat units of the formula (1) averaged, a value of 0.9 to 1.9 and d has an average value of 0.05 to 1.0 over all repeat units of the general formula (1),
• silicone resins (E) contain at most 7 wt .-% Si-bonded hydroxyl groups
• silicone resins (E) have a molecular weight M w of more than 2,500 g / mol and at most 10,000 g / mol, with the proviso that the silicone resins (E) at least 1.5 times the molecular weight M w of the silicone resin intermediates (A )
• Silicone resins (K) having a molecular weight M w of from 5.000 g / mol to 50.000 g / mol, with the proviso that the silicone resins (K) are at least 1.2 times that of
• silicone resin (K) 0.01-3% by weight of all radicals are Si-O bonded radicals derived from the polyhydric alcohol (F) in bonded form, 3 - 10 wt -.% Of all Si-bonded radicals in the silicone resin (K) is a radical -OR 2 , where R 2 is a Ci-C 6 alkyl radical
• silicone resins (K) contain at most 5% by weight of hydroxyl groups.
• the invention is reacted with high molecular weight silicone resin according to the invention, wherein the reaction is carried out in each case with an acidic condensation catalyst imparting acidity to the reaction preparation and water.
• the process according to the invention differs from the process according to US Pat. No. 4,749,764 in the use of a mixture of at least two different alkoxy-functional oligomers instead of just one such oligomer according to US Pat. No. 4,749,764 A and in the process according to the invention lower amounts of the multifunctional oligomers
• the conversion is preferably by equilibrium shift to the required extent advanced, but at the same time avoiding gelling due to excessive condensation.
• the amount of water (B) used in the first process step is stoichiometrically chosen to be sufficient to hydrolyze the desired amount of -OR 2 groups.
• Silicone resin intermediates are present. It is further preferred for the same reasons that only one alcohol R 2 OH is used, whose radical R 2 is identical to the radical R 2 of the bound to the silicone resin R 2 0 groups.
• Si-bonded alkoxy groups and optionally hydroxy-bearing silicone resin intermediates from repeat units of the formula (1) are prepared by hydrolysis and condensation processes according to the prior art from chlorosilane precursors, alkoxysilane precursors or mixtures thereof.
• hydrolysis and condensation processes according to the prior art from chlorosilane precursors, alkoxysilane precursors or mixtures thereof.
• the mixture acidity-imparting catalyst (C) is preferably selected to react under the conditions of Distillation is not decomposed, but is volatile, so that it is partially removed by distillation in this process,
• Silicone resin intermediates of the formula (1) is used.
• substitution pattern that is to say, for example, with regard to the nature and amount of the radicals R, such as the methyl or phenyl groups, or the type and number of functional groups -OR 2 , such as the methoxy or ethoxy groups. You can also do so in the substitution pattern, that is to say, for example, with regard to the nature and amount of the radicals R, such as the methyl or phenyl groups, or the type and number of functional groups -OR 2 , such as the methoxy or ethoxy groups. You can also do so in the substitution pattern, that is to say, for example, with regard to the nature and amount of the radicals R, such as the methyl or phenyl groups, or the type and number of functional groups -OR 2 , such as the methoxy or ethoxy groups. You can also do so in the substitution pattern, that is to say, for example, with regard to the nature and amount of the radicals R, such as the methyl or phenyl groups, or the type and number of functional groups
• a preferably has at least 40% and
• b has averaged over all repeat units of the general formula (1) an average value of preferably from 0.15 to 1.6 and preferably from 0.20 to 1.5,
• the radical -OR 2 is preferably added to
• Repeating units of the formula (1) may not necessarily be present. They are formed during the reaction by hydrolysis of the necessarily present alkoxy groups.
• Selected examples of radicals R are alkyl radicals such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
• Pentyl radical hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical, and isobutyl radical;
• Octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical, cycloalkyl radicals, such as Cyclopentyl, cyclohexyl,
• alkenyl radicals such as the vinyl radical
• aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radical
• alkaryl radicals such as tolyl radicals, xylyl radicals and ethylphenyl radicals
• aralkyl radicals such as the benzyl radical, the ⁇ - and the ⁇ -phenylethyl radicals , but this list is not intended to be limiting.
• the radical R is preferably unsubstituted
• Hydrocarbon radicals having 1 to 12 carbon atoms Hydrocarbon radicals having 1 to 12 carbon atoms
• methyl, ethyl and n-propyl radical and phenyl radical particularly preferably the methyl, ethyl and n-propyl radical and phenyl radical, in particular the methyl, n-propyl and phenyl radicals
• hydrocarbon radical R 2 examples are those for R
• radicals where radical R 2 is preferably a hydrogen atom or a hydrocarbon radical having 1 to 6 carbon atoms, preferably a hydrogen atom, the
• Methyl or ethyl radical in particular is the methyl radical, this list is not limiting.
• acids which can be used as acidic catalysts (C) are preferably mineral acids such as hydrochloric acid, nitric acid or phosphoric acid, with hydrochloric acid being particularly preferred owing to its volatility, polyacids such as polyphosphoric acid, C TiTlOr ⁇ TH htt- ⁇ a -FP ⁇ a np nH pr I lr örrnpn preferably carboxylic acids such as formic acid, acetic acid,
• Adipic acid, benzoic acid, phthalic acid, citric acid can be used.
• the acidic catalysts (C) are used in amounts of
• Hydrochloric acid HCl or solid acid catalysts may be added as an aqueous solution to the reaction mass.
• concentration of these aqueous solutions is 5 to 35% by weight, preferably 10 to 30% by weight, in particular 20 to 25% by weight.
• the silicone resin intermediates of repeating units of the formula (1) have molecular weights Mw (weight average) in the range of 600 to 2500 g / mol, preferably with one
• Example numbering abbreviated as SM) from repeat units of the formula (1) are reproduced here below, the list being to be understood as illustrative and not restrictive:
• Me 2 Si0 2/2 units wherein the ethoxy groups are distributed over the specified structural units.
• Si-bonded methoxy carries on the surface and which consists on average of 99 mol% MeSi0 3/2 units and 1 mol% Me 2 Si0 2/2 units, wherein the alkoxy groups are distributed over the specified structural units.
• the first method step is preferably at a
• the first step in the pressure of the surrounding atmosphere ie, about 1020 hPa, carried out, but it can also be carried out at higher or lower pressures.
• the first process step produces silicone resins (E) from repeat units of the formula (2)
• R c is Si (OR 1 ) d O ( 4-cd) / 2 (2), where R and R 1 are as defined above and c is preferably present in at least 40% and preferably in at least 50% of all repeat units of the formula (2 ) has the value 1 and can also have the value 1 in 100% of all repeating units of the formula (2), and c over all
• a has an average value of preferably 0.08 to 0.90 and preferably 0.10 to 0.80, averaged over all repeat units of the general formula (1),
• Weight percent more preferably at most 4
• Silicon intermediates from repeat units of the formula (2) may not be present. They are formed during the reaction by hydrolysis of the necessarily present alkoxy groups.
• the silicone resin intermediates of repeating units of the formula (2) have molecular weights Mw (weight average) in the range of more than 2,500 g / mol and at most 10,000 g / mol with a polydispersity of preferably at most 25 and are preferably liquid.
• Repeating units of the formula (1) and the silicone resins of repeating units of the formula (2) is at least 1.5 times of the silicone resin intermediate
• stepwise increase in molecular weight from stage to stage is a particular and essential feature of the process of the invention. If the increase in molecular weight reported here is not achieved, then the performance of the end products described later in the Examples will not be achieved. In particular, not the
• the silicone resins (E) are obtained from repeat units of the formula (2) obtained in the first step in the presence of a polyhydric, at least three carbon-bonded OH-carrying alcohol (F ) further condensed to give the final product according to the invention.
• Alcohols having three to four C-bonded OH groups, preferably three C-bonded OH groups, are preferably used as the polyhydric alcohols (F).
• Hydrocarbon radical having 5 to 25 carbon atoms which is optionally interrupted by one or more heteroatoms, preferably oxygen atoms and carbonyl groups, means and
• x is an integer from 3 to 20, preferably 3 to 4, preferably 3.
• polyhydric alcohols (F) containing at least 3 C-bonded OH groups are trimethylolethane,
• Trimethylolpropane ditrimethylolpropane, glycerol,
• Pentaerythritol and polyols according to formula (4)
• R 5 and R 7 denote the same or different, monovalent, linear, branched or cyclic aliphatically saturated
• Hydrocarbon radicals which comprise 2 to 15 carbon atoms and which comprise at least one carbinol group, wherein the sum of the carbinol groups of the radicals R 5 and R 7 together must be at least 3. That is, when R 5 has only one carbinol group, then R 7 must simultaneously contain at least 2 carbinol groups.
• Radicals R 6 are divalent linear, branched, cyclic or aromatic hydrocarbon radicals having 2 to 12
• radicals R 5 and R 7 are HO (CH 2 ) 2 -; HO (CH 2 ) 3 -; H 3 C-CH (OH) -CH 2 -; HO-H 2 CC (CH 3 ) 2 CH 2 -; (HIGH,) 3 C-CH 2 -; H 3 C-C (CH 2 OH) 2 CH 2 -; HO-H 2 C-CH (OH) -CH 2 -; H 5 C 2 - C (CH 2 OH) 2 - CH 2 -.
• Preferred are as small as possible, so as few as possible
• polyhydric alcohols containing at least three C-bonded OH groups (F) are preferred, which dissolve in water or in methanol to at least 50 wt .-% solids content, in particular those which are at least 50 wt .-% dissolve in water.
• Preferred examples are triethylolethane,
• Trimethylolpropane ditrimethylolpropane and glycerin. Particularly preferred examples are ditrimethylolpropane and
• Trimethylolpropane A most preferred example is trimethylolpropane.
• Silicone resins (K) from repeat units of the formula (3):
• R, c and d are as defined above,
• R 4 is the same or different and is a radical R 2 , where R 2 is a Cx-Cg-alkyl radical,
• R 4 is a monovalent radical R 3 ', wherein R 3 ' is from the polyvalent, at least three C-linked OH groups
• R 4 is a bridging radical R 3 *, where R 3 * bridged two or more repeat units of the formula (3) via two or more -OR 4 groups and of the
• R 3 * preferably a bivalent to polyvalent hydrocarbon radical having 5 to 25 carbon atoms, optionally by one or more Heteroatoms, preferably oxygen atoms and carbonyl groups, is interrupted and which optionally also contains one or more OH groups,
• Si-bonded radicals 3 - 10 wt .-% of all Si-bonded radicals is a radical -OR 4 , in which R 4 is a Ci-C 6 alkyl radical R 2 , and at most 5 wt .-% Si-bonded hydroxyl groups are included.
• Radicals R 4 in the silicone resin (K) of the formula (3) are radicals of the type R 2 , where R 2 is a C 1 -C 6 -alkyl radical,
• R 4 can be a monovalent radical R 3 ', where R 3 ' is preferably a C 5 -C 25 -alkyl, C 5 -C 25 -cycloalkyl, or optionally a cyclic alkyl group comprising C 5 -C 25 -Aralkylrest which is optionally interrupted by one or more heteroatoms and which optionally contains one or more OH groups means
• R 4 can be a bridging radical R 3 *, where R 3 * is preferably a C 5 -C 25 -alkylene, C 5 -C 25 -cycloalkylene radical bridging two or more repeating units of the formula (3) optionally a C 5 -C 25 -aralkylene radical comprising a cyclic alkyl moiety, optionally substituted by one or more
• Heteroatoms preferably oxygen or carbonyl, is interrupted and optionally contains one or more OH groups, means.
• radicals R 3 'and the radicals R 3 * bridging two or more repeat units of the formula (3) are formed by the reaction of the silicone resins (E) from repeat units of the formula (2) with the polyvalent, at least 3 C-bonded OH radicals.
• Group-bearing alcohols (F) These lead to
• Silicone resin repeating units of the formula (3) crosslinking units or terminally bonded units that still have carbon-bonded OH groups.
• Si-bonded radicals 3-10% by weight of all the Si-bonded radicals are an OR 4 radical in which R 4 is Cx-Cg-alkyl radical R 2 , with the radical R 4 being used in these cases Methyl and the ethyl radical is particularly preferred, especially the methyl radical.
• R 4 is Cx-Cg-alkyl radical R 2
• Methyl and the ethyl radical is particularly preferred, especially the methyl radical.
• 3.0-9.5% by weight of all Si-bonded radicals are an OR 4 radical in which R 4 is a monovalent C 1 -C 6 -alkyl radical R 2 , particularly preferably 3.5-9.0% by weight. -%, In particular 3.5 - 8.5 wt .-%.
• the units OR 4 are preferably not more than 4
• Silanol groups need not be present in the silicone resins (K) from repeating units of the formula (3). They may arise during the reaction by hydrolysis of the necessarily present alkoxy groups even when used in the preparation
• the amount of water (G) is again at least so that they stoichiometrically for the amount to be hydrolyzed
• Alkoxy groups is sufficient.
• the alcohol formed during the condensation is optionally distilled off in a mixture with water in order to shift the equilibrium of the condensation reaction to the side of the condensates.
• the second stage is preferably carried out using an inert solvent (J).
• the inert solvent is added at the beginning of the second stage embodiment in such an amount that the mixture of silicone resin (K) of repeating units of the formula (3) and the inert solvent taken alone gives a 40 to 90% solution would, ie a solution containing 40 to 90% by weight of resin and correspondingly 60 to 10% by weight of inert
• such an amount of the inert solvent is metered in that one as just
• the second process step is preferably at a
• the second step in the pressure of the surrounding atmosphere ie about 1020 hPa, carried out, but it can also be carried out at higher or lower pressures.
• the acid used during the second stage if it is volatile, preferably during the distillation of
• Propelled solvent or optionally neutralized by neutralization with a suitable base Any resulting salt is removed by filtration.
• a volatile acid is selected, in particular hydrochloric acid, which is expelled during the distillation, so that no
• Suitable bases for neutralization are alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal siliconates such as
• Sodium siliconate and potassium siliconate such as trimethylamine, ethylamine, diethylamine, triethylamine and n-butylamine, ammonium compounds such as
• Tetramethylammonium hydroxide Tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, benzyltrimethylammonium hydroxide, alcoholates such as
• Natrim ethoxide and sodium ethoxide are particularly preferred.
• the molecular weight M w of the silicone resins (K) of repeating units of the formula (3) is preferably at least
• stepwise increase in molecular weight from stage to stage is a particular and essential feature of the process of the invention. If the increase in molecular weight reported here is not achieved, then the performance of the end products described later in the Examples will not be achieved. In particular, not the
• the silicones (K) of repeating units of the formula (3) have molecular weights Mw (weight average) in the range from 5,000 to 50,000 g / mol, preferably having a polydispersity of not more than 25. They are preferably highly viscous liquid or solid as pure resins. They are characterized by high storage stability, wherein the storage stability can optionally be further improved by the addition of stabilizers. Suitable stabilizers (L) are those which react with the remaining acid traces or with remaining traces of water. They are preferably liquid or in the resins (K) according to the invention
• stabilizers (L) which react with traces of acid are, for example, epoxy-functional compounds, such as epoxidized soybean oil, amines, such as trialkylamines, for example tri-n-octylamine or triisooctylamine.
• epoxy-functional compounds such as epoxidized soybean oil
• amines such as trialkylamines, for example tri-n-octylamine or triisooctylamine.
• Water scavengers are acetals of the acetone, such as 2,2-dimethoxypropane and 2, 2-dimethyl-1,3-dioxolane.
• High molecular weight silicone resins (K) are particularly suitable for use in anticorrosive preparations. In particular, they are suitable for use for the purpose of corrosion protection at high temperature.
• the high molecular weight silicone resins prepared by the process according to the invention also for the purpose of high-temperature resistant corrosion protection.
• Corrosion protection of reinforcing steel used in reinforced concrete wherein the compounds of the invention can be used both in pure form and in preparations here. Corrosion-inhibiting effects in reinforced concrete are achieved both when bringing the compounds or preparations according to the invention containing them into the concrete mixture before they are brought into shape and
• Silicone resins contain serve, such as:
• Control of the rheological properties of the preparation containing the high molecular weight silicone resins prepared by the process of the invention Control of mechanical properties, such as
• Flexibility, scratch resistance, elasticity, ductility, flexing ability, tear behavior, rebound behavior, hardness, density, tear propagation resistance, compression set, behavior at different temperatures, coefficient of expansion, abrasion resistance and other properties such as
• High molecular weight silicone resins prepared according to the present invention or composition containing them contains control of electrical properties, e.g.
• high molecular weight silicone resins according to the invention can in Preparations with appropriate selection of the preparation components also as an additive for the purposes of defoaming, flow-promoting, hydrophobing, hydrophilization,
• the high molecular weight silicone resins prepared by the process according to the invention can be incorporated in liquid or in hardened solid form in elastomer compositions. Here, they may for the purpose of enhancing or improving other performance characteristics, such as the control of transparency, heat resistance, yellowing tendency, or
• Weathering resistance can be used.
• the silicon atom is tetravalent.
• the refractive indices are in the wavelength range of
• the transmission is determined by UV VIS spectroscopy.
• a suitable device is, for example, the Analytik Jena Specord 200.
• the measurement parameters used are: Range: 190 - 1100 nm Increment: 0.2 nm, Integration time: 0.04 s, Measurement mode:
• a quartz plate attached to a sample holder (dimension of the quartz plates: HxB about 6 7 cm, thickness about 2.3 mm) is placed in the sample beam path and measured against air. Thereafter, the sample measurement takes place.
• HxB dimension of the quartz plates: HxB about 6 7 cm, thickness about 2.3 mm
• the molecular compositions are by means of
• NMR Nuclear Magnetic Resonance
• Spectrometer Bruker Avance I 500 or Bruker Avance HD 500
• Probe head 5 mm BBO probe head or SMART probe head (Bruker)
• Pulprog zg30
• NS 64 or 128 (depending on the sensitivity of the
• Sample head 10 mm lH / 13C / l5N / 29Si glass-free QNP probe head
• Pulprog zgig60
• the glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated Tigel, heating rate 10 K / min.
• the particle sizes were measured by the method of dynamic light scattering (DLS) with determination of the zeta potential.
• the following aids and reagents were used for the determination:
• the sample to be measured is homogenized and filled bubble-free into the measuring cuvette.
• the measurement is carried out at 25 ° C after a equilibration time of 300s with high resolution with automatic measurement time adjustment.
• an aqueous hydrochloric acid solution prepared by mixing 4.20 g of 20% aqueous HCl solution with 92 g of deionized water. The dosage of this aqueous hydrochloric acid preparation takes 10 min.
• the mixture becomes cloudy and heats up slightly, with the observed exotherm under the chosen conditions being 4 ° C, so that the final temperature after dosing is 23 ° C. It is then heated to a reflux rate of 65 ° C at a heating rate of 40 ° C / h. The mixture clears during heating. It holds for 2 h at reflux.
• the mixture is cooled to room temperature. 3.80 g of a 30% strength sodium methylate solution in methanol are subsequently metered in. The mixture is then pH neutral.
• the volatiles are at 80 ° C and 10 mbar
• Residue is then diluted with xylene to give an 80% solution in xylene, i. the preparation contains 80% of the silicone resin and 20% xylene.
• the residual methoxy content of the resin is 6.55 wt. % and is thus more than 50% lower than the average methoxy content of the starting mixture of 14.01% by weight.
• Mw 3800 g / mol
• Mn 1300 g / mol
• polydispersity PD 2.9.
• Mw is more than twice as high as in the case of the silicone resin intermediates SM 1 and SM 4 used.
• the molar composition is:
• the solution which was obtained after filtration, proves to be stable in viscosity and thus stable on storage in a drying oven (4 weeks at 60 ° C.).
• Dropping funnels under nitrogen are 1800.0 g of the 80% first stage xylene silicone resin solution of this
• Example containing 1440.0 g of silicone resin, so 0.38 mol of resin mixed with 28.8 g (0.21 mol) of trimethylolpropane (2% based on the silicone resin in the 1800.0 g of solution).
• the mixture is cloudy.
• the silicone resin contains 6.55% by weight of methoxy groups (MeO- with molecular weight 31 g / mol), so that in 1440 g of silicone resin
• the mixture remains cloudy, an exotherm ie is not observed under the selected conditions.
• the temperature of the mixture is after completion of addition of hydrochloric acid 22 ° C.
• the mixture is cooled to room temperature. 3.31 g of a 30% strength sodium methoxide solution in methanol are subsequently metered in. The mixture is then pH neutral.
• the volatiles are at 150 ° C and 10 mbar
• the residual methoxy content of the resin is 5.38% by weight.
• the molar composition is:
• PhSi0 3/2 28.6%
• the solution obtained after filtration proves to be viscous and thus storage stable for more than 4 weeks at 60 ° C. when stored in a drying oven.
• the first stage in this example is not isolated, but implemented immediately in the second step.
• Silicone resin intermediates SM 1 (alkoxy content 14.2% by weight,
• the mixture becomes cloudy and heats up slightly, with the observed exotherm under the chosen conditions being 4.6 ° C, so that the final temperature after dosing is 27.5 ° C.
• the mixture is then heated at a heating rate of 40 ° C / h to 80 ° C jacket temperature.
• the mixture clears during heating. It is now within 3 min to a vacuum of 300 mbar and starts with distilling off the resulting methanol in a mixture with a little water. Within 50 minutes 16.48 kg of distillate are removed. The distillate contains 99% methanol and 1% water.
• silicon-bonded methoxy groups is determined to be 7.01% by weight and is thus still half of the average
• the vacuum is broken, the heating set and
• Trimethylolpropane which corresponds to 1.98% by weight of the calculated amount of resin from the first step. This results in a Si-OR: COH ratio of 5.1: 1.
• the HCl content of the reaction mixture is 140 ppm after xylene addition.
• 2370.82 g of aqueous hydrochloric acid solution prepared by mixing 25.82 g of 20% aqueous HCl solution with 2345 g of deionized water are added over 5 minutes.
• the residual methoxy content of the resin is 6.10 wt
• the solution turns out after addition of 1000 ppm of epoxidized soybean oil (available under the name DRAPEX 39 Fa. Galata Chemicals, 68623 Lampertheim, Germany) to the amount of silicone resin when stored in a drying oven for more than 4 weeks at 60 ° C stable.
• epoxidized soybean oil available under the name DRAPEX 39 Fa. Galata Chemicals, 68623 Lampertheim, Germany
• the first stage is not isolated and here a particularly robust procedure is chosen, which is in a special way for
• the mixture clears during heating. It is distilled until an internal temperature of 120 ° C was reached (3.5 h).
• distillate which consists essentially of methanol (99 wt .-%) and water. This distillate can be added
• the first-stage silicone resin contains 5.98% by weight of methoxy groups (MeO- having a molecular weight of 31 g / mol), so that in the 896.3 g of silicone resin obtained, there are 83.69 g and 2.7 mol of methoxy groups, respectively available.
• Trimethylolpropane based on the silicone resin. 0.13 mol
• Trimethylolpropane corresponds to 0.39 mol of hydroxy groups, so that there is a molar Si-OMe: COH ratio of 7.0: 1.
• the organic phase consists essentially of xylene (98.1 wt .-%) in addition to a little methanol and water and can be used unchanged. The small amounts of water and methanol must be taken into account when calculating the follow-up approaches.
• the distillation residue is cooled to 60 ° C. and 108 g of xylene are added in order to adjust a solids content of 80% by weight.
• the residual methoxy content of the resin is 4.79% by weight.
• the solution obtained after filtration proves to be stable at 60 ° C. for more than 4 weeks when stored in an oven.
• the preparation comprises the steps of partial alkoxylation,
• the mixture is heated for 2 h at 67.3 ° C, which corresponds to reflux temperature.
• the stirrer is switched off and the phases are left to separate for 30 minutes with the heating off.
• the lower phase (sour water) is separated. Repeat the washing process three times with 750 ml of water each at 60 ° C and 30 min phase separation as just described. After the third wash, the residual HCl content has dropped to 5 pp.
• the organic phase is heated on a rotary evaporator at 80 ° C and 10 mbar vacuum until no more distillate is obtained.
• the resulting resin has a proportion of silicon-bonded methoxy groups of 7.43 wt .-%.
• Mw 1480 g / mol
• Mn 944 g / mol
• PD 1.57.
• Trimethylolpropane 3.7 g ethylene glycol, 0.5 g 10%
• Reaction time was a total of 5 h at 150 ° C bath temperature.
• the reaction is stopped by cooling and addition of another 140 g of xylene.
• a 50% xylene solution is obtained.
• the viscosity of the solution is 76 cSt at 25 ° C.
• the resulting resin has a proportion of silicon-bonded methoxy groups of 4.52 wt .-%. Based on the initial amount of 7.43 wt .-% methoxy groups, these are 60.83%, which have been retained, or a conversion rate based on
• the molar composition is:
• Solvent a sticky film. After 24 hours, the film is still not tack-free. A tack-free surface is obtained only after 35 hours. The film has an uneven texture

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• 2017
  • 2017-11-27 KR KR1020197025164A patent/KR20190104229A/ko active IP Right Grant
  • 2017-11-27 EP EP17804200.8A patent/EP3559134B1/de active Active
  • 2017-11-27 JP JP2019546290A patent/JP2020512432A/ja active Pending
  • 2017-11-27 WO PCT/EP2017/080556 patent/WO2019101349A1/de unknown
  • 2017-11-27 CN CN201780087507.7A patent/CN110392720A/zh not_active Withdrawn
  • 2017-11-27 US US16/482,761 patent/US20210292483A1/en not_active Abandoned

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